Canadian Metallurgicd Quarrerly, Vol 36. No. 2, pp.

121-130, 1997
0 1997 Published by Elsevier Science Ltd
Pergamon Printed in Great Bntam. All rights reserved
00084433/97 $17.00+0.00

PII: SOOOt+4433(96)00039-0

THERMODYNAMIC ANALYSIS OF THE SODA ASH

SMELTING OF LEAD ACID BATTERY RESIDUE IN A
ROTARY FURNACE
A. GUERRERO, A. ROMERO, R. D. MORALES and F. CHAVEZ
Metallurgical and Materials Department, Instituto Politecnico National-Esiqie, A.P.75-874,
D.F. 07300 Mexico

(Receined 25 June 1995; in rekedform 30 August 1996)

Abstract-A thermodynamic analysis of the rotary furnace process for the recovery of lead from battery
residue by carbothermic reduction with soda ash (Na,CO,) was performed. Suitable models were selected
to represent the thermodynamic behaviour of the bullion, matte, slag and gas phases. Equilibrium con-
siderations and mass balances were performed in order to determine the effect of input parameters such as
carbon and soda ash additions on the lead recovery. The processing of battery residue is characterized
chemically by two distinct regimes, oxidizing and reducing, the occurrence of which depends on the amount
of reductants added (carbon and iron). A maximum in the lead is predicted by the model at a critical range
of concentration of reductants, which depends on the Pb, PbSO,, PbS and PbO, contents of the charge.
The thermodynamic model was adapted to the rotary furnace process to diminish the lead in the discarded
matte-slag from 5-8 wt.% Pb to about l-2 wt.% Pb. A 20% excess of carbon was added to achieve the
highest lead recovery. It was found that by increasing the Fe/Fe,O, mass ratio in the iron chips from 119
to 7/3 the slag viscosity diminished and the furnace operation became closer to the equilibrium condition.
0 1997 Published by Elsevier Science Ltd

R&sum&On a execute une analyse thennodynamique du procede en fourneau de recuperation du plomb

de residue de batteries par reduction carbothermique avec de la soude calcinee (NazCOJ. On a choisi des
modtles approprits pour rep&enter le comportement thermodynamique des phases de metal, de matte,
de laitier et de gaz. On a execute des considerations d’equilibre et des balances de masse afin de determiner
l’effet des parametres d’alimentation tels que des additions de carbone et de soude calcinee sur la recuper-
ation du plomb. Le traitement de residue de batteries est caracterise chimiquement par deux regimes
distincts, oxydation et reduction, dont l’occurrence depend de la quantitt d’agents rtducteurs ajoutes
(carbone et fer). Le modtle prtdit un maximum de plomb dans une region critique de concentration
d’agents reducteurs, qui dependent du contenu de la charge en Pb, en PbS04, en PbS et en PbOz. On a
adapt6 le modele thermodynamique au pro&de du fourneau rotatif afin de diminuer le contenu en plomb
de la mattelaitier, qui est rejectee, de 5-8% en poids de Pb a environ l-2%. Un exces de 20% de carbone
a permis d’obtenir la recuperation de plomb la plus &levee. On a trouve qu’en augmentant le rapport de
masse de Fe/Fe,O, dans les copeaux de fer de l/9 a 713, la viscosite du laitier diminuait et l’operation du
fourneau se rapprochait de la condition d’equilibre.

INTRODUCTION increased by improved control of the metallurgical reactions

The treatment of materials for the recovery of heavy metals
imposes many processing and environmental challenges. This
is particularly important for the lead recycling industries, whose
main source of lead is scrapped lead-acid batteries [l]. There
are several processes for recycling batteries but the pyr-
ometallurgical processes are still the most suitable for large-
scale lead recycling. Recent years have seen the emergence of
several new high intensity lead smelting processes such as Out-
okumpu [2], Kivcet [3], Isasmelt [4] and QSL [S]. These devel-
opments have been encouraged by the increasingly restrictive
government regulations on in-plant hygiene, as well as by the
need to reduce capital and operating costs. These new processes
will become economically and environmentally viable in the
coming decades. However, the traditional blast furnace, rever-
beratory and rotary furnaces are still commonly used in many
plants.
The production of lead in the recycling processes can be
121
and also by the optimization of furnace operation, such as
feed materials preparation and furnace tapping. Processes for
converting lead sulfate or lead sulfide are still currently being
investigated so as to optimize aspects which include sulfur diox-
ide pollution abatement and lead recovery. The investigation
reported in this work represents one such effort, where the goal
was to perform a thermodynamic analysis of the rotary furnace
process to improve the extraction of lead metal from acid bat-
teries and from other lead-containing materials.
PROCESS DESCRIPTION
The main secondary lead smelting companies in Mexico have
one blast furnace and several rotary furnaces. Scrap batteries
are fed into the blast furnace together with the required fluxes
and components to produce the bullion. One of the by-products
of this furnace is a dust which is mainly composed by lead
122 A. GUERREROet al.:SODAASH SMELTING OF LEAD ACID BATTERY RESIDUE
Fig. 1.Simplified
flowsheet
of themainMexicanleadsecondary
sulfide.The rotary furnacesare usedto processscrapbatteries,
drossanddust by-productsfrom the blastfurnace.A flow sheet
of the secondaryleadmetallurgyprocessin Mexico is shownin
Fig. 1.
Rotary furnace feedstocksare divided into lead-bearing
materials,flux and reductant components.The former is lead
battery scrapwhich is composedof approximately 66wt. % Pb,
14.7wt.% PbOl, 12.1wt. % PbS04, in addition to plastic and
acid components;blast furnace dust which contains from
60wt.% to 80wt.% PbS; recycled drosseswith high metallic
lead content, usually greater than 30wt.% Pb, together with
other metallic (antimony and calcium)and non-metallicspecies
collected in the refining processsuch as PbS. The non-lead-
bearingmaterialsare sodaash (Na,CO,) which is capableof
fixing the noxious sulfur dioxide emissionsin the slagphase;
coke(85% fixed carbon) andiron chips(composedof a mixture
of Fe and FezO,)to perform the carbothermicreductionof lead
sulfateand leadoxide.
The rotary furnace processtakes place at temperatures
between900” and 1000°Cby the combustionof a mixture of
natural gas and oxygen. The phasesproduced in the process
are: bullion, matte, slagand gas.The bullion is mainly formed
by leadand, when the chargehasa high drosscontent, thereis
alsoantimony (l-3 wt.%). The matte consistsof metal sulfides.
The slagmay contain metal oxides, carbonatesand sulfates.
The gas phaseis formed by CO*, CO, 02, S2, SOr, SO, and
small amountsof PbO,,, and PbS,,,, as well as the products
generatedby the combustion of oxygen and natural gas.
Together with these phases,solid speciessuch as carbon,
metallic iron, cementite(Fe&Z)and magnetite(Fe,O,) are also
present.
industries
for recyclinglead-acidbatteries.
THERMODYNAMIC ANALYSIS
Thermodynamicevaluationshave beenrecentlymadeto esti-
matethe effect of input parameterson the leadrecovery in lead
smeltingreactors [69]. Someof them are basedon stability
diagramsto explainthe roleplayedby eachspecies in the system
[6, 71;otherstake into accountthe activity data availablein the
literature [8, 91,which are usually valid at a given temperature
and composition. Our approach is based on the ther-
modynamicsof solutionsand equilibrium calculationswhich
are employedto predict the behaviourof the systemover a wide
rangeof temperaturesand compositions.
The thermodynamicanalysisof the rotary furnaceprocessis
rather complexdue to the componentsand phasesthat mustbe
considered.The first step was to selecta suitable model to
representthe thermodynamicbehaviourof eachphaseand then
to choosea method to calculate the equilibrium conditions
which take into accountall the componentsand phasesof the
system.Thus, the compositionof eachphasecan be estimated
from the equilibrium conditions. The following assumptions
weremadeto simplify the thermodynamicapproach:
1. Thermodynamicequilibrium is attainedduring the process.
2. The bullion is formed by Pb and Sb. Other metallic species
are neglected.
3. The matte is a chemicalsolution of FeS, Na,S, PbS and
Sb$,.
4. The slagis a mixture of two typesof ions.There are cations
(Fe’+, Fe3+, Sb3+,Pb2+,Na+) occupying sitesin a cation
sublatticeand anions(02-, CO:-SO:-) occupying sitesin
an anion sublattice.
 A. GUERRERO et al.: SODA ASH SMELTING OF LEAD ACID BATTERY RESIDUE 123

Table 1. Thermodynamic properties relative to elements at 298.15 K; H (Jjmol) = A+ Cpd r; S (J/molK) = B + ,,[i,, (CM’W-
*9 i .I5
Cp = (Jjmol K) = a+b(10-3)T+c(105)i’~2+d(10~6)TZ+e(109)T~3

Component A B a b c d e
-
Pb (1) 3811 70.513 32.489 - 3.088 0.0 0.0 0.0
Fe (4 8260 35.959 23.991 8.360 0.0 0.0 0.0
Sb (1) 17531 62.708 31.380 0.0 0.0 0.0 0.0
c 6) 0 5.740 0.109 38.940 - 1.481 - 17.385 0.0
PbO (I) - 198438 75.119 64.383 0.0 0.0 0.0 0.0
PbOz 6) - 274470 71.797 63.216 31.016 - 8.979 - 13.991 0.0
PbSO, (I) - 896221 124.442 184.096 0.0 0.0 0.0 0.0
PbS (I) - 70028 104.027 61.923 0.0 0.0 0.0 0.0
Fe0 (I) -261069 55.413 68.199 0.0 0.0 0.0 0.0
Fe203 (1) - 195421 23.265 35.1 0.0 - 13.328 0.0 0.12563
Fe,C (4 23685 103.593 107.194 12.552 0.0 0.0 0.0
FeS (I) - 74670 76.437 71.128 0.0 0.0 0.0 0.0
Na,O (1) - 372790 91.724 104.600 0.0 0.0 0.0 0.0
NG03 (1) -1126619 113.357 189.535 0.0 0.0 0.0 0.0
Na,SO, (1) - 1368299 154.129 197.401 0.0 0.0 0.0 0.0
NG (1) -351775 93.964 92.048 0.0 0.0 0.0 0.0
SW, (1) - 669073 167.780 156.900 0.0 0.0 0.0 0.0
Sb,% (1) - 173685 205.463 167.360 0.0 0.0 0.0 0.0
-

5. The gasphasecontains02, CO, CO*, S2,S02, S03, PbO,,, Table 2. Excess free energy for the bullion and matte sub-systems
and PbS,,,. gE= i i [x,x,(a,,+b,,T)lJlmol
‘=I,=,
The gasphasecan beconsideredasan ideal solution,however,
condensedphasesform solutionsthat are not ideal. In such System (A-B) i i aii hi
cases,it is necessaryto have accessto proven solution models
Pk+Sb 1 1 - 1074.00 -1.18
and reliablesolution data. In this work, the excessfree energy NaS1/2-FeS 1 1 - 147928.00 80.83
for the bullion and matte phaseswere representedby poly- 1 2 33489.00 0.0
nomialsin termsof the mole fractions of the components[lo]; NaS1/2-PbS 1 1 - 18828.00 0.0
and the slagwas representedby a sub-latticemodel [ll]. The SbS,,,FeS 1 1 15646.00 0.0
SbS,,,-PbS 1 1 1374160.00 - 1883.00
thermodynamicpropertiesof the puresubstances in this system, FeS-PbS 1 1 0.0 0.0
listedin Table 1, weretaken from Barin [12], exceptfor PbSO,
and Fe,O,. For the solidPbS04,the enthalpy, entropy and heat
capacity weretaken from Barin [12], and the meltingpoint and
valuesof AH”,, and ASor,,at the meltingpoint weretaken fromthesesub-binary systems was madepreviously [17]. The par-
Jacob and Toguri [13]. Data for Fe203were taken from the ametersfor the excessfree energiesare listed in Table 2. Once
databasesof the thermodynamicpropertiesof the F*A*C*T the Gibbs energiesof the binary systemsare obtained, the
system[141. next stepis to follow an interpolation procedurebasedon the
solutionmodelto estimatethe Gibbsenergyof this quaternary
Solution model for the bullion
phasefrom thoseof the binary phases.The interpolation pro-
The Gibbs free energyof mixing for the PbSb liquid phase cedureusedin this work is the method proposedby Kohler
isexpressedby:
V81.
A,,‘, = R~X,lnX,+XalnX,]+gE (1) Solution model for slag
where, A two-lattice model[111,one for cationsand onefor anions,
is approximatedfor the slagphase.The modelassumes that all
1 the cationshave anionsas nearestneighboursand vice versa.
In an ideal solution, cations and anions are randomly dis-
The PbSb phasediagram[1.51and liquid activities reported tributed on the cation sublatticeand anion sublattice,respec-
by Hultgren et al. [161showthat PbSb solutionsslightly depart tively. The ideal molar Gibbs free energyof mixing for the A-
from the ideal behaviour; thus, the very smalladjustablepar- B binary systemwith onecommonion is expressedas:
ameters,a,, and b,, listedin Table 2, are required.

Solution model for the matte

The Gibbs free energy of mixing usedpreviously in eqn (1)
can also be used to representthe sub-binary systemsin the (3)
matte by expressingthe componentsin terms of FeS, PbS, wherem and n representthe number of molesof ions that go
NaSIIZ and SbS,,,. A critical evaluation of available data for into a given sublatticewhen one moleof A and onemole of B
124 A. GUERRERO et al.: SODA ASH SMELTING OF LEAD ACID BATTERY RESIDUE

Table 3. Excess free energy for the slag sub-systems Table 4. Composition of charges A and B expressed in terms of Pb=,,
SE = (qA+eXd 2 i [YAY~(a,,+6,,T)lJlmol Charge A mass ratio Charge B mass ratio
‘=,,=I species/Pb,,, species/Pb,,,
Component
System (A-B) qA qB i j % bz,
Pb 0.7584 0.7264
Na@-NazS04 2 2 1 1 0.0 0.0 PbOz 0.1692 0.1297
Na,SO,PbSO, 2 2 1 1 - 18896.00 12.98 PbSO, 0.1390 0.1065
Fe@Fe,O, 2 6 1 1 - 2929.00 0.0 PbS 0.0000 0.1023
PbO-Fe203 2 6 1 1 - 6276.00 0.0 SW3 0.0000 0.0112
PbO-Sb,O, 2 6 1 1 -25104.00 0.0 Na2C03 0.1127 0.1265
PbO-PbS04 2 2 2 1 - 11225.00 0.0 Fe 0.0563 0.0632
2 2 1 2 - 16225.00 0.0

are added to the solution, respectively. For example, in the

Na,S04-PbS04 system, m = 2 and n = 1, since one mole of recycled drosses. Table 4 lists the composition of each chemical
species in both charges.
Na2S04 produces two moles of Na+ and one mole of PbSO,
produces one mole of Pb’+. The molar excess free energy in
charge-asymmetrical systems is usually expressed in terms of Calculations for charge type A
equivalent fractions:
Figure 2 illustrates the effect of carbon on the amount of lead

gE= (%~*+qaXa) i=lj=l

i i
[
Y~Yga,j+b,,T)
1 (41
produced and the species content in the slag/matte phase for
charge A. The mass of each species is expressed per mass of
total lead in the charge. This figure shows clearly that without
where, carbon there is a relatively high fraction of recovered lead;
with small additions of carbon, around C/Pb,,, = 0.004, lead
%&A recovery increases almost to one; then, between 0.004 and 0.01
Y, = =1-Y,
CL&* + CMB ‘T’bm> lead sulfide becomes more stable and the lead in bullion
diminishes; finally, the lead content is gradually increased up
ai, and b,, are empirical parameters. The factors qA and qB are
to one with a further increase of carbon content. The calculated
the number of equivalents per mole of component. For example,
values of species content in the slag/matte phase show that the
qNaZSo4 = 2 and qPbsO4= 2. The factor (qAXA+qBXB) in eqn (4) minimum lead concentration in the bullion is related to the
is the number of equivalents per mole of solution.
maximum PbS content, and that some species are stable only
The empirical coefficients alj and b, are found by the sim- over a limited range of carbon content.
ultaneous optimization of the thermodynamic and phase diag-
The calculated equilibrium concentrations at 950°C shown
ram data [ 171. Table 3 shows the values of these parameters for in Fig. 2, can be used to deduce the global reactions that take
the sub-binary systems whose thermodynamic data are avail-
place at various carbon contents.
able. The interpolation formulae for estimating Gibbs energy
of the multicomponent slag from binary Gibbs energies were a) Without carbon the reactions that occur are
also based on the Kohler equations [181. PbS04 + Na2C03
The general free energy minimization method is used to esti-
mate the equilibrium concentration. For a given set of con- = PbO+Na2S04+C0,AGo = -1.4kJ/mol (6)
straints (such as fixed temperature, pressure and overall PbO, + Fe = PbO + Fe0 AGo = - 247.8 kJ/mol (7)
concentration) the free energy minimization algorithm finds the
set of mole numbers of each species as well as the compositions b) Between 0 and 0.004 C/Pbr,,, metallic lead and iron oxide
of all solution phases which globally minimize the free energy are formed by the reaction:
function. This is the equilibrium phase assemblage. The pro- 2Pb0, + 2Fe + C = 2Pb + 2FeO + CO,
gram SOLGASMIX written by Eriksson [ 191 is used to perform
the equilibrium calculations for the rotary furnace process. This AC’ = - 564.93 kJ/mol (8)
program is a part of the CSIRO Thermochemistry System [20]. c) Between 0.004 and 0.01 C/PbTot, the lead recovery
decreases since lead sulfide is produced:
3Na,S04 + 2Pb + Fe0 + SC = 2PbS + FeS + 3Na2C03 + 2C02
EQUILIBRIUM CALCULATIONS AGO = - 249.54 kJ/mol (9)

The efficiency of lead recovery mainly depends on the carbon d) With a carbon content higher than 0.01 C/PbTO,, PbS is
again reduced by the reaction:
content, thus the following calculations were performed in order
to estimate the distribution of species in each phase as a function Na,SO, + PbS + Fe0 + 2C = Pb + FeS + Na,S + Na2C03 + CO*
of carbon added in the charge. Two kinds of charges, usually
AGO = - 464.72 kJ/mol (10)
processed in the plant, are considered: (A) with only scrap
batteries and (B) with scrap batteries as well as leady dust and The calculations show that practically all the sulfur is retained
 A. GUERRERO er al.: SODA ASH SMELTING OF LEAD ACID BATTERY RESIDUE 125

1
V Pb

0.04 z
I’ %
I’
\
0.03 2
C \
0 0.9 y PbS
6
s
\
0.02 g
\
s - c
\ .A d
2 0.85 .PbO \ 9
. 0.01 a
\ . .
\ 1
0.8
0.12

0.08 I/-\ Na,CO,

1

0
0.08

Fe&
.

0 0.02 0.04 0.08 0.08

c lPbot

Fig. 2. Calculatedequilibriumcomposition,
expressedasmassratios,of a systemusingscrapbatteries
(chargetypeA) at 950°C.

in the condensedphasesassulfateor sulfide,with a negligible
formation of S1,SOz,SO3and volatile lead species.O’Connell
et al. [21] carried out smeltingtestsat 1000-l 100°Cwith scrap
batteries having a composition in weight percent: 6% Pb,
54.22%PbS04, 10.9%PbO, 19% PbO, and 9.88% plasticand
acid components. Their experimental results and the cal-
culations performed by the thermodynamic analysisof this
work are in good agreement,asshownin Fig. 3. In both cases,
the %Pb recovery plotted asfunction of the C/PbTotratio exhi-
bits a maximum.
126 A. GUERRERO et al.: SODA ASH SMELTING
65--
g’”
80) 55--
u oxidizing and reducing regimes, there is a sharp redistribution
2 of antimony where all of the Sb2S3 reacts to produce metallic
8 antimony which reports to the bullion. It can also be seen in
40--
25--
0 0.02 0.04 0.06 0.06 0 and the lead in matte-slag phases. In this example, iron ranges
W'bro,
Fig. 3. Effect of carbon addition on the lead recovery using only scrap
batteries in the charge at 1100°C. Experimental points are from O’Con-
nell et al. [21]. Solid line was calculated in the present work.
Calculations for charge type B
As was mentioned previously, the rotary furnace processes
scrap batteries and some other materials. The by-products con-
sidered in this work are the leady-dust produced in the lead
blast furnace and antimonial drosses obtained in the refining
operation. To show the application of the thermodynamic cal-
culations, the composition of the charge shown in Table 4 was
selected. The mass of each species, including iron, carbon and
Na,CO,, is expressed per mass of total lead in the charge.
The iron addition was 0.0632 Fe/Pb,,,, soda ash was 0.1265
NG03/PbTo,, and carbon ranged from 0 to 0.08 C/Pb,,,,. The
Fe,O, content in the iron chips is neglected. Figure 4 illustrates
the effect of carbon on the amount of lead produced and the
species concentration in the slag/matte phase. It can be seen
that two distinct regimes occur. The first is oxidizing, at low
carbon contents, and the second is reducing, at high carbon
contents, The range of carbon content which separates both the
regimes can be considered as that which gives the maximum
amount of lead sulfide; in this example is was from 0.016 to
0.020 C/PbTO,. Reaction (9) proceeds with the formation of PbS
in this range of carbon content.
In the oxidizing region (C/Pb,,,<0.016) sodium sulfate is
produced through the reaction between PbS04 and Na&O+
Between 0.016 and 0.020, sulfur is no longer forming sulfate
species and only PbS is present. With a higher carbon content
(reducing region), the process can be explained by an overall
reaction: Na,C03 and PbS react with Fe and C to produce
Na,S, FeS, Pb and CO.
Na,CO, + 2PbS + Fe + 2C
=Na,S+FeS+2Pb+3COA@ = -102.47kJ/mol (11)
OF LEAD ACID BATTERY RESIDUE
Both iron and carbon are reductants and have a combined
effect to produce metallic lead. The difference between these
elements is that the iron added to the charge is still present at
the end as iron oxide or iron sulfide; while most of the carbon
is consumed to produce gaseous products (CO and CO1).
Antimony recovery
The antimony recovery can also be predicted assuming the
same composition of charge B. The calculated results are shown
in Fig. 5 and indicate that at low carbon contents, the antimony
is mainly present as Sb2S3. At the transition region between the
Figs 4 and 5, that PbS and Sb2Sx disappear approximately at
the same carbon content. A similar sharp transition for Pb was
experimentally observed by O’Connell et al. [21] in car-
bothermic reduction tests of scrap battery.
Lead recovery
The above mentioned charge composition was used to estab-
lish the combined effect of carbon and iron on the lead recovery
from 0 to 0.06 Fe/Pb,,, and carbon from 0.0268 to 0.0333
Wbm; the results are plotted in Fig. 6. This figure shows that
there is a critical composition range of reductant components
(C and Fe). Below this range, lead sulfide is a main component
in the matte. On the other hand, with a slightly higher content
of carbon and iron, the theoretical lead concentration in the
matte diminishes almost to zero and the fraction of lead recov-
ery increases up to 0.999.
EXPERIMENTS AND RESULTS
A program to design charge compositions in the rotary fur-
nace process, based on the above mentioned thermodynamic
analysis, has been established in some Mexican plants [22]. The
first challenge in calculating the furnace charge was to estimate
the analyses of the various feedstocks. The following average
mass composition of the leady materials were obtained:
a) Scrap battery: 66% Pb, 14.7% PbOz and 12.1% PbSO,
b) Leady dust: 65% PbS, 25% C
c) Dross: 40% Pb, 30% PbS and 30% Sb2S3
Two kinds of iron chips were used:
a) 10% Fe and 90% Fe,O,; b) 70% Fe and 30% Fe,O,
Before the model was adapted to the process, the average charge
was approximately 10 tonnes, with invariably 1000 kg of
Na,C03, 400 kg coke and 300 kg iron chips (10% Fe and 90%
Fe,O,). The temperature of the process ranged from 940°C to
980°C. The slags produced usually had a high concentration of
magnetite (Fe,O,), which was separated as a magnetic product.
This phase is identified by X-ray diffraction analysis as shown
in Fig. 7. The viscosity of the slag was increased with the
magnetite content and thus, the efficiency of the separation of
phases, bullion and slag, was diminished. The slag-matte phases
produced by the foregoing explanation of furnace operation
contained between 5 and 8% Pb.
 A. GUERRERO ef al.: SODA ASH SMELTING OF LEAD ACID BATTERY RESIDUE 127

1 0.2

0.96 0.16
E

0.s 0.1 0

cc?

0.65 0.06

0
0.15 , _-

Fig. 4. Calculated equilibrium composition (in terms of mass ratios) of a system using scrap batteries,
leady-dust and drosses (charge type B) at 950°C.

A group of 10 experiments was carried out in the furnace analysis in order to obtain less than 1% Pb in the slag-matte
with charge compositions approximately the same as those of phase. Best results were obtained with 20% excess of carbon.
the conventional process. In these experiments, the carbon and Iron chips composed of 70% Fe and 30% Fe,O, were used
iron contents were estimated according to the thermodynamic to prevent the formation of Fe,O,, and therefore to reduce the
128 A. GUERRERO et al.: SODA ASH SMELTING OF LEAD ACID BATTERY RESIDUE

1.2

0.4

0.2

0
0 0.02 0.04 0.06 0.08 0.1
C 1 Pb,, 0 0.02 0.04 0.06
Fig. 5. Antimony distribution between bullion and matte at 950°C using 0.16
a charge with antimonial dross (charge type B).

slag viscosity. The charge compositions of these experiments

are listed in Table 5. Figure 8 shows the experimental lead
percent in the (slag + matte) for the previous metallurgical 0.12
practice and the process with optimized charges, as well as the E 0’0.0333 CIPb
values predicted by the thermodynamic analysis of this work.
% + 0.0300 ClPb
It is clear that the employment of iron chips richer in metallic .
V 0.0268 C/Pb
iron provides lower lead concentrations in the slag which are
3
nearer to the thermodynamic calculations. 2 0.08
Figure 9 presents the statistical results of the lead content in ?
slag for 80 tests with the old furnace operation and 30 tests with 8
the optimized process. It is clear that the charges designed with
s
the thermodynamic analysis have produced slags with less than
2 wt.% Pb in more than 85% of the charges. 2
- 0.04

DISCUSSION

The fundamentalassumptionmadein the simulationis that

thermodynamicequilibriumisattained. Thisis appropriatedue 0 II

to the long processtime (around 4 h) and the rotary motion of 0 0.02 0.04 0.06
the furnace. However, the calculated and experimentallead Mass Ratio Fe I Pb TO,
recoveriesmay be different when the solid magnetiteis pre-
cipitated. The formation of magnetiteincreasesthe slag vis-
cosity and interfereswith the separationof the metallic lead Fig. 6. Predicted lead recovery (upper graph) and lead content in the
and the slag. discarded matte-slag phases (lower graph) at 950°C in terms of the
carbon and iron contents using charge type B.
As far asthe industrial application is concerned,the rotary
furnace charge may be optimized using the equilibrium cal-
culationsasdiscussed below:
not be worth continuing increasingthe carbon in the charge.
Minimizing the utilization of certain reagents, especially carbon
Similarly, the stoichiometricNa,CO, content can alsobe pre-
and Na,Co3 dicted from thesefigures.However, a 20% excessof Na,CO,
Figure 6 showsthat there is an asymptotic behaviour once may be suggested to increaseslagfluidity which isan important
the fraction of lead recovery reaches0.999. Thus, it would parameterduring the tapping process.
 A. GUERRERO et al.: SODA ASH SMELTING OF LEAD ACID BATTERY RESIDUE 129

Optimized Process
Old Furnace Operation

I I I I I I 1 1
20 30 40 50 60 70 80 9( 1

2 8 (DEGREES)
Fig. 7. X-Ray Diffraction pattern of the magnetic part of the slag.

El I I I I I I III1

*
7 - * A .
Ir

11
* 123456789
6 - * wt % Pb IN SLAG
.
Fig. 9. Frequency distribution of experimental lead content in slag +
matte phases.

2 4 - reduced to metallic iron or Fe&. Thus, although Fig. 6 shows

d that high carbon and iron content in the charge is advisable for
a high lead yield, the metallic iron, iron carbide and the non-
f, 3-
consumed carbon may increase melt viscosity, hindering the
a"
w phase separation. On the other hand, if low carbon and iron
2 - I additions are made, the slag will be in an iron deficient state.
I
I Thus, chemical attack of the slag pots, which are constructed
1 -
8 8 ' 8 I of plain carbon steel, will be promoted.
8 8

l a l ’ l Minimizing the evolution of solid magnetite

0 7 7 l???lI
12 3 4
EXPERIMENT
Fig. 8. Lead content in slag + matte phases: l Calculated values with
the present model and W experimental values obtained with the charge
compositions given in Table 5 (iron chips are 70 wt.% Fe, 30 wt.%
Fe*O,). A Experimental results obtained for charges with constant
carbon (400 kg) and iron chips (300 kg) with the composition 10 wt.%
Fe, 90 wt.% Fez03.
It has been shown elsewhere [22] that a low Fe/Fe,03 ratio
5 6 7 B 9 lo
NUMBER
(about l/9) in the iron scrap promoted the formation of solid
magnetite which increased the slag viscosity and hence inter-
fered with reaching the equilibrium conditions in the furnace.
A much higher lead recovery (about 98%) was obtained by
using iron chips composed of 70% Fe and 30% Fe203.
CONCLUSIONS

Maximizing consumption of particular
The composition of the charge depends on the available fur-
nace feedstocks. Therefore, the amount of battery scrap, leady-
dust and drosses must change from charge to charge. It is
important to optimize the reactants (C, Fe and Na,C03) to give
the highest lead recovery for a given charge.
Generating a matte-slag combination known to have a high
chemical stability
This aspect is directly related to the carbon and iron contents
in the charge. If excess carbon is added, a portion of the iron
that was provided for the FeS and Fe0 can be carbothermically
feedstocks A thermodynamic analysis of the rotary furnace process for
the recycling of lead was made to study the effect of soda ash and
reductant additions. The process is characterized chemically by
two distinct regimes, oxidizing and reducing, the occurrence of
which depends on both the amount of reductant and the lead
species contained in the charge. The calculations show that
there is a sharp transition between the regimes. Matte is formed
mainly by lead sulfide and antimony sulfide in the oxidizing
region, whereas in the reducing region most of the lead and
antimony are in the bullion. On the other hand, the transition
point requires an appropriate ratio of reductants.
The thermodynamic model was adapted to the rotary furnace
130 A. GUERRERO et al.: SODA ASH SMELTING OF LEAD ACID BATTERY RESIDUE

Table 5. Weight of the charge components in the experiments

Component 1 2 3 4 5 6 I 8 9 10

Pb 2912.10 2901.60 2827.20 3438.60 3462.90 3349.20 3599.40 2999.10 2743.20 2998.50
PbS04 953.53 966.64 1014.39 1038.71 1029.56 1057.00 1070.95 968.89 823.34 967.00
PbOl 1441.42 1382.17 1791.59 1384.63 1307.29 1339.17 1367.85 1424.77 1302.92 1837.57
PbS 603.40 422.70 505.45 705.30 764.55 450.35 805.20 599.15 868.25 1068.65
NaZCO, 900.00 900.00 900.00 900.00 900.00 925.00 1100.00 900.00 900.00 1000.00
C 512.55 492.15 490.45 594.15 489.60 463.25 533.80 539.75 511.70 509.15
Fe 210.00 270.00 267.00 294.00 310.00 308.00 365.00 374.00 345.00 473.00
Fe203 90.00 115.00 114.00 126.00 133.00 132.00 157.00 160.00 148.00 203.00

process to diminish the lead in the discarded matte-slag from 7. Chulu, B. L. and Martins, G. P., EPD Congress 1993, (edited by
5-8 wt.% Pb to about l-2wt.% Pb. A 20 percent excess of J.P. Hager), pp. 981-999, 1993.
8. Espeleta, A. K., Hino M. and Yazawa, A., Pr0c.H.H. Kellog Inter-
carbon and Na,CO, was added to achieve the highest lead nntional Symposium, (edited by N.J. Themelis and P.F. Duby), pp.
recovery. It was found by increasing the Fe/Fez03 ratio in the 127-144. Harriman N.Y., 1991.
iron chips from l/9 to 7/3 that the slag viscosity diminished 9. Weenik, E. M., Puy, E. R. and Duyvestyn, W. P. C., in Lead and
and the furnace operation more closely approached chemical Zinc 90, (edited by T.S. Mackey and R.D. Prengaman), pp. 597-
606. The Minerals, Metals and Materials Society, Anaheim Ca.,
equilibrium. 1990.
10. Rao, Y. K., Stoichiometry and Thermodynamics of Metallurgical
AcknowledgementsThe authors are very indebted to the institutions Processes, Cambridge Univ. Press, 1985.
CONACyT, SNI and IPN-COFAA for the permanent support of the 11. Pelton, A. D., CALPHAD, pp. 127-142. 1987.
process metallurgy activities at IPN-ESIQIE. 12. Barin, I., Thermochemical Data of Pure Substances, ed. VCH Ver-
lagsgesellschaft, 1989.
13. Jacob, K. T. andToguri, J. M., Met. Trans.B., 1978,9B, 301-306.
14. Bale, C. W., Pelton, A. D. and Thompson, W. T., FCA*C*T
REFERENCES (Facility for the Analysis of Chemical Thermodynamics), Ecole
Polytechnique. Montreal, 1992.
15. Massalski, T., Binary Alloy Phase Diagrams, Metals Park, Ohio:
1. Queneau, P. Q., Cregar, D. E. and Mickey, D. K., Proc. Inter. Am. Sot. of Metals, 1986.
Symp. on Primary and Secondary Lead Processing, pp. 145-177. 16. Hultgren, R., Desai, P. D., Hawkins, D. T., Gleiser, M., Kelly,
Halifax, Nova Scotia 1989. K.K. and Wagman, D. D., Selected Values of the Thermodynamic
2. Sulanto, J. K., in Lead and Zinc 90, (edited by T.S. Mackey and Properties of the Elements and Binary Alloys, Metals Park, Ohio:
R.D. Prengaman), pp. 817-824. The Minerals, Metals andMaterials Am. Sot. of Metals, 1973.
Society, Anaheim Ca., 1990. 17. Guerrero, A., MSc. thesis, Instituto Politecnico National-ESIQIE.
3. Moriya, K., in Lead and Zinc 90, (edited by T.S. Mackey and Mexico, 1995.
R.D. Prengaman), pp. 23-38. The Minerals, Metals and Materials 18. Kohler, F., Monatsh Chemie, pp. 738. 1960.
Society, Anaheim Ca., 1990. 19. Eriksson, G., Chemica Scripta, pp. 106135. 1975.
4. Matthew, S. P., McKean, G. R., Player, R. L. and Ramus, K. E., 20. Turnbull, A. G. and Wadsley, W., The CSIRO-STGE Thermodata
in LeadandZinc 90, (edited by T.S. Mackey and R.D. Prengaman), System, CSIRO, Inst. of Energy and Earth Resources. Port Mel-
pp. 889-901. The Minerals, Metals and Materials Society, Anaheim bourne, Australia, 1985.
Ca., 1990. 21. O’Conell, G. J., Toguri, J. M., Pickles, C. A. and Smith, D., Proc.
5. Arthur, P., Siegmund, A. and Schmidt, M., Proc. SavardjLee Inter. Inter. Symp. on Primary and Secondary Lead Processing, pp. 195
Symp. on Bath Smelting, pp. 127-146. TMS, Montreal, Canada, 209. Halifax, Nova Scotia, 1989.
1992. 22. Chavez, F., Morales, R. D., Romero, A. and Guerrero, A., Third
6. Willis, G. M., in Lead-Zinc-Tin’80, (edited by J.M. Cigan, T.S. International Symposium on Recycling of Metals and Engineered
Mackey and T.J. O’Keefe). pp. 457-477, The Minerals, Metals and Materials, pp. 337-347. TMS, Point Clair Alabama, Nov. 12-15,
Materials Society, 1980. 1995.